US4554388A - Process for isomerization and transalkylation of alkylphenols - Google Patents
Process for isomerization and transalkylation of alkylphenols Download PDFInfo
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- US4554388A US4554388A US06/577,849 US57784984A US4554388A US 4554388 A US4554388 A US 4554388A US 57784984 A US57784984 A US 57784984A US 4554388 A US4554388 A US 4554388A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by exchange of hydrocarbon groups, which may be substituted, from the same of other compounds, e.g. transalkylation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
Definitions
- This invention relates to a process for isomerization and transalkylation of alkylphenols and for phenolderivatives in the presence of a catalyst comprising ironoxide (s) and at least one additional oxide and in the case of 2,4,6-trimethylphenol and 2,4-dimethylphenol as alkylphenol feed, of ironoxide (s) or of a catalyst comprising ironoxide (s) and at least one additional oxide.
- GB-PS No. 695 464 discloses a process in which the use of aluminum silicate and of mixed oxides of silicon, beryllium, magnesium, aluminum, zirconium and titanium for isomerizations and transalkylations of alkylphenols is described.
- a process has been found for isomerization and transalkylation of alkylphenols and/or phenol derivatives b reacting the alkylphenols and/or phenol derivatives, optionally in the presence of phenol, at temperatures of 200°-550° C., pressures of 1-300 bar (at reaction temperature) and residence times of 0,1-10 hours in the presence of metal oxides as catalyst, characterized in that the process is carried out in the presence of
- Preferred reaction conditions are 250°-450° C., 10-150 bar (at reaction temperature) and residence times of 0,5-7 hrs.
- the reaction can be carried out continuously or discontinuously.
- Useful technical reactors are tubular reactors, the tubes of which are filled with pelletized or granular catalyst. However the catalyst can also be applied in different shapes.
- the inventive process can also be carried out in fluid bed systems, using a grinded catalyst. These procedures and devices are known to the artisan.
- inventive isomerizations and transalkylations of alkylphenols and phenolderivatives are preferrentially carried out in the presence of phenol, but they can also be carried out in the presence of other added phenolderivatives, for example of cresols or anisol.
- reaction can be carried out in the gas phase, the liquid phase is generally preferred.
- Working up of the reaction product can be carried out by conventional separation processes like distillation, extraction and cristallyzation.
- the residue which remains after these separation procedures can be recycled to the isomerization and transalkylation process, leading to an almost complete conversion of the residue, optionally after having separated resinous material.
- table 1 has been carried out with a catalyst consisting of Fe 2 O 3 /SiO 2 /Cr 2 O 3 /BaO with a Fe 2 O 3 -portion being higher than 90% by weight.
- Residence time was 1-4 hours.
- hydrogen was applied with a pressure of 1 and 30 bar (at normal temperature).
- Reaction temperature was 400° C.
- the feed is shown.
- the residue was a product which could not be distilled at 190° C. and 3 mbar.
- 67,32 weight-% were methylated phenols with more than two methyl groups.
- the second column from the right side represents the total amount of desired, economically valuable mono- and dimethylphenols.
- the column at the right side represents the quantity of phenol consumed.
- the feed was a residue taken from a technical phenol alkylation unit, from which mono- and dimethylphenols had been essentially distilled off.
- the table shows that with the catalyst used, after a residence time of 4 hours, a product can be obtained, which consists of 41,62 weight-% of mono- and dialkylphenols (27,9 weight-% of mono-methyl phenols) dispatchied by a decrease of higher alkylphenols of 34,7 weight-% and of the residue of 40,8 weight-%. Comparable results are obtained, if anisol is added instead of phenol.
- Table 3 shows examples with various inventive catalysts and as a comparative example the reaction with Fe 3 O 4 as catalyst without addition of a further oxide.
- the comparative example indicates the effect of an additional oxide.
- the quantity of iron oxide (s) in the catalyst generally amounted to at least 60 weight-%. Lower quantities of iron oxide (s) lead to inferior results.
- the ratio of phenol to alkylphenol was 50:50 weight-%.
- the quantities of products shown in the tables are specified in weight percent.
- Table 6 containes comparative examples with Al 2 O 3 /SiO 2 and a catalyst consisting of mixed oxides without iron oxide (s). This catalyst consisted predominantly of nickel oxide and small amounts of SiO 2 , Cr 2 O 3 and K 2 O.
Abstract
This invention relates to a process for isomerization and transalkylation of alkylphenols and for phenol-derivatives in the presence of a catalyst comprising ironoxide (s) and at least one additional oxide and in the case of 2,4,6-trimethylphenol and 2,4-dimethylphenol as alkylphenol feed, of ironoxide (s) or of a catalyst comprising ironoxide (s) and at least one additional oxide.
Description
(1) Field of the Invention
This invention relates to a process for isomerization and transalkylation of alkylphenols and for phenolderivatives in the presence of a catalyst comprising ironoxide (s) and at least one additional oxide and in the case of 2,4,6-trimethylphenol and 2,4-dimethylphenol as alkylphenol feed, of ironoxide (s) or of a catalyst comprising ironoxide (s) and at least one additional oxide.
(2) Description of the Prior Art
Isomerization and transalkylation of alkylphenols in the presence of acidic catalysts are known for a long time. GB-PS No. 695 464 discloses a process in which the use of aluminum silicate and of mixed oxides of silicon, beryllium, magnesium, aluminum, zirconium and titanium for isomerizations and transalkylations of alkylphenols is described.
In DE-OS No. 18 04 632 isomerizations and transalkylations are disclosed with mixed catalysts consisting of alumina and silicic acid.
The known processes however are not satisfactory with regard to technical scale operation, since the conversion to desirable products from an economical point of view, for example to monoalkylphenols, 2,6-resp. 2,4-dimethylphenol or 2,3,6-trimethylphenol is relatively low. This is also the case if alkylphenols comprising several alkyl groups, are converted in the presence of phenol.
Effective, technically useful catalysts, which permit the isomerization and transalkylation of alkylphenols with up to five alkyl groups and alkylphenols mixtures, which additionally contain residues originating from technical units, in the presence of relatively small amounts of added phenol in order to obtain useful products are not known. With the catalysts of the state of the art only negligible amounts of residues are converted to desirable products.
According to the present invention, a process has been found for isomerization and transalkylation of alkylphenols and/or phenol derivatives b reacting the alkylphenols and/or phenol derivatives, optionally in the presence of phenol, at temperatures of 200°-550° C., pressures of 1-300 bar (at reaction temperature) and residence times of 0,1-10 hours in the presence of metal oxides as catalyst, characterized in that the process is carried out in the presence of
(a) iron oxide (s)
(b) at least one oxide selected from the groups consisting of
1. B, Al, Ce
2. Si, Ge, Sn, Ti, Zr
3. Cr, V
4. Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Mn, La.
Furthermore a process has been found for isomerization and transalkylation of 2,4,6-trimethylphenol and/or 2,4-dimethylphenol by reacting these alkylphenols in the presence of phenol and/or alkylated phenols at temperatures of 200°-550° C., pressures of 1-300 bar (at reaction temperature) and residence times of 0,1-10 hours in the presence of metal oxide (s), characterized in that the process is carried out in the presence of a catalyst consisting of iron oxide (s) or of a catalyst consisting of iron oxide (s) and at least one oxide selected from the groups consisting of
1. B, Al, Ce, Ga, In, Sc, Y
2. Si, Ge, Sn, Pb, Ti, Zr, Hf
3. Cr, V, Nb, Ta, Mo, W, Re, Co, Ni, Ru, Ir
4. Li, Na K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Mn, La, Ca, Zn, Cd
Preferred reaction conditions are 250°-450° C., 10-150 bar (at reaction temperature) and residence times of 0,5-7 hrs. The reaction can be carried out continuously or discontinuously. Useful technical reactors are tubular reactors, the tubes of which are filled with pelletized or granular catalyst. However the catalyst can also be applied in different shapes. The inventive process can also be carried out in fluid bed systems, using a grinded catalyst. These procedures and devices are known to the artisan.
The investigations of applicant have shown that it is of advantage to work under inert gas pressure, for example in a hydrogen atmosphere, nitrogen, CO2 or steam atmosphere. Thus addition of water can be advantageous.
The inventive isomerizations and transalkylations of alkylphenols and phenolderivatives are preferrentially carried out in the presence of phenol, but they can also be carried out in the presence of other added phenolderivatives, for example of cresols or anisol.
Although the reaction can be carried out in the gas phase, the liquid phase is generally preferred. Working up of the reaction product can be carried out by conventional separation processes like distillation, extraction and cristallyzation. The residue which remains after these separation procedures can be recycled to the isomerization and transalkylation process, leading to an almost complete conversion of the residue, optionally after having separated resinous material.
The following examples and tables illustrate the invention in more detail.
The examples of table 1 have been carried out with a catalyst consisting of Fe2 O3 /SiO2 /Cr2 O3 /BaO with a Fe2 O3 -portion being higher than 90% by weight.
Residence time was 1-4 hours. As an inert gas, hydrogen was applied with a pressure of 1 and 30 bar (at normal temperature). Reaction temperature was 400° C. In the first line the feed is shown. In all examples a mixture of 20 weight-% of phenol and 80 weight percent of a mixture of methylphenols and residue of a technical phenol-alkylation unit was used. The residue was a product which could not be distilled at 190° C. and 3 mbar. 67,32 weight-% were methylated phenols with more than two methyl groups. The second column from the right side represents the total amount of desired, economically valuable mono- and dimethylphenols. The column at the right side represents the quantity of phenol consumed. As a whole (without added phenol) the feed was a residue taken from a technical phenol alkylation unit, from which mono- and dimethylphenols had been essentially distilled off.
The table shows that with the catalyst used, after a residence time of 4 hours, a product can be obtained, which consists of 41,62 weight-% of mono- and dialkylphenols (27,9 weight-% of mono-methyl phenols) accompagnied by a decrease of higher alkylphenols of 34,7 weight-% and of the residue of 40,8 weight-%. Comparable results are obtained, if anisol is added instead of phenol.
At a residence time of 1 hour and a hydrogen pressure of 30 bar, 33,63 weight-% of mono- and dialkylphenols (23,6 weight-% monomethylphenols) are obtained, accompagnied by a corresponding decrease of residue. At a residence time of 1 hour and 30 bar of hydrogen pressure, 33,71 weight-% of mono- and dimethylphenols are obtained.
TABLE 1
__________________________________________________________________________
Product composition, weight-%
higher o-,m-,p-,Cr
phenol
resicence
bar
Ph.
T o- m- p- 2,4-
2,6-
methyl
dist.
2,4-
con-
catalyst
time hrs
H.sub.2
feed
°C.
Ph cresol
cresol
cresol
DMP DMP phenols
residue
2,6-DMP
sumed
__________________________________________________________________________
feed 20,0
0,06
0,01
0,12
1,71
0,14
67,32
10,64
2,04 --
Fe.sub.2 O.sub.2 :
1 1 20 400
7,83
11,56
7,58
4,07
7,22
3,28
43,36
15,1
33,71 60,85
SiO.sub.2
Cr.sub.2 O.sub.3 :
BaO-
100:2:
1:1
Fe.sub.2 O.sub.2 :
1 30 20 400
9,54
13,92
6,21
3,44
7,11
2,95
51,63
5,2 33,63 52,3
SiO.sub.2
Cr.sub.2 O.sub.3 :
BaO-
100:2:
1:1
Fe.sub.2 O.sub.2 :
2 30 20 400
8,04
13,23
8,17
4,43
8,47
4,34
47,12
6,2 38,64 59,8
SiO.sub.2
Cr.sub.2 O.sub.3 :
BaO-
100:2:
1:1
Fe.sub.2 O.sub. 2 :
4 30 20 400
8,12
13,24
9,68
5,0 9,04
4,66
43,96
6,3 41,62 59,4
SiO.sub.2
Cr.sub.2 O.sub.3 :
BaO-
100:2:
1:1
Fe.sub.2 O.sub.2 :
2 50 20 400
8,85
14,38
6,87
3,64
7,87
3,35
52,24
2,8 36,11 55,75
SiO.sub.2
Cr.sub.2 O.sub.3 :
BaO-
100:2:
1:1
Fe.sub.2 O.sub.3 :
2 50 400
anisol
SiO.sub.2 : feed 21,2
0,05
0,01
0,11
1,70
0,13
66,87
9,93 --
Cr.sub.2 O.sub.3 :
2 50 400
phenol
14,41
7,01
3,68
7,93
3,36
52,13
2,64
36,39 55,46
BaO 8,84
__________________________________________________________________________
Comparative examples are shown in table 2. with conventional catalysts.
The example, carried out with so-called white pearls (Al2 O3 /SiO2) is to be compared with the example of table 1, where a residence time of 2 hours has been applied.
The result demonstrates that the quantity of mono- and dialkylphenols obtained, decreases from 38,64 weight-% (25,83 monomethylphenols) in the total product to 30,09 weight-% (20,2 weight-% monomethylphenols), accompagnied by an increase of non-distillable residue to 25,7 weight-%, whereby 73,25 weight-% of added phenol is consumed.
Also the use of γ-Al2 O3 leads to a considerably lower yield with regard to mono- and dialkylphenols (18,56 weight-% of monomethylphenols).
TABLE 2
__________________________________________________________________________
Product composition, weight-%
higher o-,m-,p-,Cr
resicence
bar
Ph.
T o- m- p- 2,4-
2,6-
methyl
dist.
2,4-and
phenol
catalyst
time hrs
H.sub.2
feed
°C.
Ph cresol
cresol
cresol
DMP DMP phenols
residue
2,6-DMP
consumed
__________________________________________________________________________
white-
pearls
Al.sub.2 O.sub.3,
2 30 20 400
5,35
7,53
9,09
3,59
6,78
3,10
38,86
25,7
30,09 73,25
(10%)
SiO.sub.2
(90%)
α-
2 30 20 400
8,62
8,56
4,83
5,17
8,14
2,54
53,34
8,8
29,24 56,9
Al.sub.2 O.sub.3
__________________________________________________________________________
Table 3 shows examples with various inventive catalysts and as a comparative example the reaction with Fe3 O4 as catalyst without addition of a further oxide.
The comparative example indicates the effect of an additional oxide.
TABLE 3
__________________________________________________________________________
Product composition, weight-%
p- higher o-,m-,p-,Cr
phenol
resicence
bar
Ph.
T o- m- cre-
2,4-
2,6-
methyl
dist.
2,4-
con-
catalyst
time hrs
H.sub.2
feed
°C.
Ph cresol
cresol
sol
DMP DMP phenols
residue
2,6-DMP
sumed
__________________________________________________________________________
-- -- -- -- -- 20,0
0,06
0,01
0,12
1,71
0,14
67,32
10,64
2,04 --
Fe.sub.2 O.sub.3 :SiO.sub.2 :
2 30 8,04
13,23
8,17
4,43
8,47
4,34
47,12
6,2 38,64 59,8
Cr.sub.2 O.sub.3 :BaO
100:2:1:1
Fe.sub.2 O.sub.3 :SiO.sub.2 :
2 30 6,79
12,51
8,16
4,33
9,16
4,68
46,57
7,8 38,84 66,05
Cr.sub.2 O.sub.3 100:4:1
Fe.sub.2 O.sub.3 :SiO.sub.2 :
2 30 7,39
13,21
7,78
4,28
8,86
4,16
49,32
5,0 38,29 63,05
MnO:CaO
100:2:1:0,2
Fe.sub.2 O.sub.3 :ZrO.sub.2 :
2 30 9,22
13,11
6,59
3,6
7,27
3,07
50,44
6,7 33,64 53,9
Cr.sub.2 O.sub.3 :BaO
100:2:1:1
Fe.sub.2 O.sub.3 :SiO.sub.2 :
2 30 7,99
13,12
6,76
3,78
7,56
3,6 46,69
10,5
34,82 60,05
V.sub.2 O.sub.5 :BaO
100:2:1:0,2
Fe.sub.3 O.sub.4
2 30 16,33
7,31
3,25
2,77
6,07
1,54
55,33
7,4 20,94 18,35
Fe.sub.2 O.sub.3 :SiO.sub.2
2 30 7,5 12,42
7,51
4,44
8,32
3,97
55,84
8,2 36,66 57,1
100:2
__________________________________________________________________________
In table 4 experimental results are shown whereby the catalyst of table 1 has been used and the same conditions as indicated in table 1, with 2,4,6-trimethylphenol as feed and the addition of 22,2 weight-% of phenol. In a comparative experiment, Al2 O3 /SiO2 (10/90 weight-%) was used. In both cases the reaction temperature was 370° C.
An example with 2,4,6-triethylphenol and 20 weight-% of added phenol is also shown in table 4.
TABLE 4
__________________________________________________________________________
Product composition, weight-%
o- higher o-,m-,p-,Cr
phenol
resicence
bar 2,4,6- cre-
m- p- 2,4-
2,6-
methyl
dist.
2,4-
con-
catalyst
time hrs
H.sub.2
TMP pH sol
cresol
cresol
DMP DMP phenols
residue
2,6-DMP
sumed
__________________________________________________________________________
2,4,6-
TMP
-- -- 370° C.
77,1
22,2
0,1
-- 0,05
0,61
0,02
0,02 -- 0,69 --
Fe.sub.2 O.sub.3 :SiO.sub.2 :
2 30 36,89
2,99
13,24
-- 5,55
28,01
10,67
0,35 2,3
57,47 86,41
Cr.sub.2 O.sub.3 :BaO
100:2:1:1
white pearls
2 30 25,76
2,75
6,44
5,36
3,46
10,52
4,98
27,23
13,5
30,76 87.5
__________________________________________________________________________
4,6-tri-
ethylphenol
pure + 20
Gew. % phenol
phenol o-ethylphenol
m-ethylphenol
p-ethylphenol
__________________________________________________________________________
Fe.sub.2 O.sub.3 :SiO.sub.2 :
2 30 2,1 12,7 -- 5,3
Cr.sub. 2 O.sub.3 :BaO
100:2:1:1
__________________________________________________________________________
2,4-diethylphenol
2,6-diethylphenol
higher ethylphenlols
2,4,6-triethylphenol
__________________________________________________________________________
Fe.sub.2 O.sub.3 :SiO.sub.2 :
29,4 9,2 7,9 33,4
Cr.sub.2 O.sub.3 :BaO
100:2:1:1
__________________________________________________________________________
Furthermore investigations of applicant have shown that surprisingly and non-obvious to the artisan, with 2,4,6-trimethylphenol and 2,4-dimethylphenol as starting materials, not only combinations of iron oxide (s) with numerous additional oxides, but also iron oxide (s) alone lead to selective isomerizations and transalkylations, whereby in contrast to the state of the art no meta-substituted phenols are obtained, however very low quantities of residue.
Results according to the instant invention with iron oxide catalysts are shown in tables 5 (feed: 2,4,6-trimethylphenol) and 6 (2,4-dimethylphenol).
The experiments have been carried out at 400° C., at a pressure of 30 bar (at normal temperature) and residence time of 2 hours.
The investigations of applicant have led to the result (not shown in the tables) that also at different temperatures, pressures and residence times, selectivities and very low quantities of residue are obtained.
The quantity of iron oxide (s) in the catalyst, generally amounted to at least 60 weight-%. Lower quantities of iron oxide (s) lead to inferior results.
The ratio of phenol to alkylphenol was 50:50 weight-%. The quantities of products shown in the tables are specified in weight percent.
In table 5 a comparative experiment is shown with Al2 O3 /SiO2 at catalyst.
The result shows that m-cresol, 2,5-dimethylphenol, 2,3-dimethylphenol and 2,3,6-trimethylphenol (all m-substituted) are formed. Furthermore 18,6 weight-% of residue were formed. Table 6 containes comparative examples with Al2 O3 /SiO2 and a catalyst consisting of mixed oxides without iron oxide (s). This catalyst consisted predominantly of nickel oxide and small amounts of SiO2, Cr2 O3 and K2 O.
The examples of table 6 clearly demonstrate that in contrast to the inventive experiments neither selectivity nor the formation of only small amounts of residue are obtained.
The same results are obtained with regard to isomerization and transalkylation of 2,4,6-trimethylphenol and/or 2,4-dimethylphenol, if these compounds contain other alkylphenols in small amounts.
The abbreviations used in the tables are:
Ph=phenol
DMP=dimethylphenol
TMP=trimethylphenol
MP=methylphenols
Cr=cresols
The experimental results summarized in the tables show the superiority of the catalysts used, according to the invention with respect to selective transformations to useful products combined with the formation of anly small amounts of residues.
In particular with 2,4,6-trimethylphenol and 2,4-dimethylphenol as feed, outstanding results are obtained.
TABLE 5
__________________________________________________________________________
Product composition, weight-%
o-,p-Cr;
phenol
o- m- p- 2,5-
2,4-
2,6-
2,3-
resid.
2,4,6-
2,3,6-
dist.
3,4-
con-
catalyst
Ph cresol
cresol
cresol
DMP DMP DMP DMP DMP TMP
TMP
resid.
3,6-DMP
sumed
__________________________________________________________________________
white pearls
11,6
13,8
15,2
6,2 9,3 8,1
4,4 3,9 4,4 2,4
2,1
18,6
325 71,0
SiO.sub.2 /Al.sub.2 O.sub.3
Fe.sub.3 O.sub.4
29,3
19,7
-- 5,9 -- 8,0
3,1 -- -- 28,9
-- 5,1 36,7 43,0
Fe.sub.2 O.sub.3 /Al.sub.2 O.sub.3
24,4
21,9
-- 7,4 -- 10,1
4,2 -- -- 24,7
-- 7,3 43,6 48,3
Fe.sub.2 O.sub.3 /
26,7
20,1
-- 7,8 -- 15,5
5,1 -- -- 22,4
-- 2,4 48,5 46,6
Cr.sub.2 O.sub.3 /SiO.sub.2 /
CaO
Fe.sub.2 O.sub.3 /MoO.sub.2
25,3
20,3
-- 6,9 -- 15,1
6,1 -- -- 25,0
-- 1,3 48,4 47,0
K.sub.2 O
Fe.sub.2 O.sub.3 /V.sub.2 O.sub.5
26,0
18,9
-- 6,4 -- 14,7
5,4 -- -- 25,1
-- 3,5 45,4 45,9
Fe.sub.2 O.sub.3 /SnO.sub.2 /
27,4
19,7
-- 7,1 -- 15,0
6,2 -- -- 23,6
-- 1,0 48,0 44,9
Na.sub.2 O
Fe.sub.2 O.sub.3 /NiO
25,9
20,1
-- 7,2 -- 15,0
6,4 -- -- 24,5 0,9 48,7 47,1
GeO.sub.2 /K.sub.2 O
Fe.sub.2 O.sub.3 /Cr.sub.2 O.sub.3
26,3
19,9
-- 8,1 -- 17,7
5,3 -- -- 22,3
-- 0,4 51,0 46,9
SiO.sub.2 /BaO
Fe.sub.2 O.sub.3 /RuO.sub.2
26,3
19,6
-- 6,8 -- 14,3
5,4 -- -- 25,2
-- 2,4 46,1 46,2
Fe.sub.2 O.sub.3 /MgO
25,5
21,7
-- 6,3 -- 15,8
6,8 -- -- 23,1
-- 0,8 50,6 47,3
SiO.sub.2 /BeO
FeO.sub.3 /MnO.sub.2
26,0
20,8
-- 6,4 -- 15,1
6,5 -- -- 23,3
-- 1,9 48,8 46,3
K.sub.2 O
__________________________________________________________________________
TABLE 6
__________________________________________________________________________
Product composition, weight-%
o-,p- phenol
o- m- p- 2,5-
2,4-
2,6-
2,3-
resid.
2,4,6-
2,3,6-
dist.
Cr.; con-
catalyst
Ph cresol
cresol
cresol
DMP DMP DMP DMP DMP TMP
TMP
resid.
2,6-DMP
sumed
__________________________________________________________________________
white pearls
12,7
13,2
17,1
5,0
8,7 6,7
2,1 2,6 1,1
2,7
28,1 69,4
SiO.sub.2 /Al.sub.2 O.sub.3
NiO/SiO.sub.2
35,1
8,6
1,1
6,1
2,4 29,5
0,5 -- -- 1,2
-- 15,5
15,2 40,7
C.sub.2 O.sub.3 /K.sub.2 O
Fe.sub.2 O.sub.3 /SiO.sub.2
32,8
19,6
-- 16,9
-- 25,3
2,0 -- -- 2,7
-- 0,7 38,5 35,3
Fe.sub.2 O.sub.3 /V.sub.2 O.sub.5
29,1
23,7
-- 18,3
-- 16,3
6,1 -- -- 3,8
-- 2,7 48,1 40,2
Fe.sub.2 O.sub.3 /B.sub.2 O.sub. 3
35,1
15,9
-- 12,7
-- 33,1
2,1 -- -- 0,5
-- 0,6 30,7 38,6
Cr.sub.2 O.sub.3 /BeO
Fe.sub.2 O.sub.3 /SiO.sub.2
36,2
18,5
-- 17,6
-- 21,5
3,8 -- -- 1,9
-- 0,5 39,9 38,3
Cr.sub.2 O.sub.3 /K.sub.2 O
Fe.sub.2 O.sub.3 /SiO.sub.2
34,5
19,9
-- 18,7
-- 18,6
3,6 -- -- 3,1
-- 1,6 42,2 40,3
MoO.sub.2
Fe.sub.3 O.sub.4
32,1
17,2
-- 15,8
-- 28,0
3,1 -- -- 3,5
-- 0,3 36,1 37,9
Fe.sub.2 O.sub.3 /SiO.sub.2
31,2
15,7
-- 16,8
-- 27,8
3,8 -- -- 2,9
-- 1,8 37,6
MnO.sub.2 /CaO
Fe.sub.2 O.sub.3 /PbO
30,0
16,7
-- 16,1
-- 28,5
3,2 -- -- 3,4
-- 2,1 36,0 43,1
Cr.sub.2 O.sub.3 /BaO
Fe.sub.2 O.sub.3 /SiO.sub.2
36,3
17,8
-- 18,1
-- 21,1
2,7 -- -- 3,1
-- 0,9 38,6 27,2
V.sub.2 O.sub.5 /BaO
__________________________________________________________________________
Claims (10)
1. A process for the isomerization and transalkylation by catalytically reacting methylated or ethylated phenols and/or phenolderivatives in the presence of phenol at temperature of 200° to 550° C., pressures of 1 to 300 bar (at reaction temperature) and residence times of 0,1 to 10 hours in the presence of metal oxides as catalyst, characterized in that the process is carried out in the presence of a catalyst comprising
(a) iron oxide (s)
(b) at least one oxide selected from at least one of the groups
1. B, Al, Ce
2. Si, Ge, Sn, Ti, Zr
3. Cr, V
4. Li, Na, K, Rb, Cs, Be, Mg, Ca. Sr, Ba, Mn, La
2. A process for the isomerization and transalkylation by catalytically reacting 2,4,6-trimethylphenol and/or 2,4-dimethylphenol in the presence of phenol and/or alkylphenols at temperatures of 200°-550° C., pressures of 1 to 300 bar (at reaction temperature) and residence times of 0.1 to 10 hours in the presence of metal oxides as catalyst, characterized in that the process is carried out in the presence of a catalyst comprising iron oxide (s) or iron oxide (s) and at least one oxide selected from at least one of the groups
1. B, Al, Ce, Ga, In, Sc, Y
2. Si, Ge, Sn, Pb, Ti, Zr, Hf
3. Cr, V, Nb, Ta, Mo, W, Re, Co, Ni, Ru, Ir
4. Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Mn, La, Cu, Zn, Cd
3. A process as claimed in claim 1 or claim 2 characterized in that the process is carried out in the liquid phase.
4. A process as claimed in claim 1 or claim 2 characterized in that the process is carried out in the presence of a catalyst, which contains at least 60 weight-% of iron oxide (s).
5. A process as claimed in claim 1 or claim 2 characterized in that the pressure range is 5-180 bar at reaction temperature.
6. A process as claimed in claim 1 or claim 2 characterized in that the temperature range is 250°-450° C.
7. A process as claimed in claim 1 or claim 2 characterized in that the residence time is 0,5-7 hours.
8. A process as claimed in claim 1 or claim 2 characterized in that the phenol added is 5-70 percent by weight of the total feed mixture.
9. A process as claimed in claim 1 or claim 2 wherein the process is carried out in an inert atmosphere.
10. A process as claimed in claim 9 wherein the inert atmosphere is hydrogen, nitrogen or a mixture thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3304663A DE3304663C1 (en) | 1983-02-11 | 1983-02-11 | Process for the isomerization and transalkylation of alkylated phenols and / or phenol derivatives |
| DE3304663 | 1983-02-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4554388A true US4554388A (en) | 1985-11-19 |
Family
ID=6190560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/577,849 Expired - Fee Related US4554388A (en) | 1983-02-11 | 1984-02-07 | Process for isomerization and transalkylation of alkylphenols |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4554388A (en) |
| EP (1) | EP0119421B1 (en) |
| JP (1) | JPS59152340A (en) |
| DE (2) | DE3304663C1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291724B1 (en) * | 1997-09-24 | 2001-09-18 | General Electric Company | Suppression of highly alkylated phenols in the catalytic alkylation reaction of phenol |
| US6593501B2 (en) | 2000-09-18 | 2003-07-15 | Asahi Kasei Kabushiki Kaisha | Process for the preparation of 2,6-xylenol |
| CN108192053A (en) * | 2018-01-25 | 2018-06-22 | 杜广新 | A kind of method that high-performance Alkylphenolic Tackifying Resin is produced using phenol waste as raw material |
| US11485694B2 (en) | 2019-02-04 | 2022-11-01 | China Petroleum & Chemical Corporation | Dealklylation and transalkylation of mixed phenols to make cresols |
| US11767280B2 (en) | 2019-02-04 | 2023-09-26 | China Petroleum & Chemical Corporation | Process for making phenol and xylenes |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476329A (en) * | 1983-04-04 | 1984-10-09 | General Electric Company | Selective alkylation of phenol to o-cresol |
| DE3406536A1 (en) * | 1984-02-23 | 1985-09-05 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | METHOD FOR CONVERTING META / PARA CRESOL MIXTURES |
| CN109954499B (en) * | 2019-04-01 | 2023-09-26 | 顾卓昳 | Phenol ortho-methylation catalyst and method for producing ortho-methylated phenol by using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB695464A (en) * | 1950-06-23 | 1953-08-12 | C U R A Patents Ltd | Improvements relating to the manufacture of phenols |
| US3519692A (en) * | 1967-02-06 | 1970-07-07 | Koppers Co Inc | Preparation of meta-rich cresols |
| US3933927A (en) * | 1970-03-16 | 1976-01-20 | Ethyl Corporation | Phenol transalkylation process |
| US4398048A (en) * | 1981-10-21 | 1983-08-09 | Uop Inc. | Preparation of 2,4,6-trialkylphenols |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1804632A1 (en) * | 1968-10-23 | 1970-06-11 | Consolidation Coal Co | Catlytic transmethylation of methyl substit - uted phenols |
| DE3100517C2 (en) * | 1980-03-29 | 1983-04-28 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | Process and catalyst for the o-alkylation of phenols |
| DE3012357C2 (en) * | 1980-03-29 | 1983-03-24 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | Process and catalyst for the ortho-alkylation of phenols |
| DE3103665C2 (en) * | 1981-02-04 | 1983-10-13 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | Process for the o-methylation of phenols and a catalyst for carrying out the process |
-
1983
- 1983-02-11 DE DE3304663A patent/DE3304663C1/en not_active Expired
-
1984
- 1984-02-03 EP EP84101092A patent/EP0119421B1/en not_active Expired
- 1984-02-03 DE DE8484101092T patent/DE3460271D1/en not_active Expired
- 1984-02-07 US US06/577,849 patent/US4554388A/en not_active Expired - Fee Related
- 1984-02-10 JP JP59022050A patent/JPS59152340A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB695464A (en) * | 1950-06-23 | 1953-08-12 | C U R A Patents Ltd | Improvements relating to the manufacture of phenols |
| US3519692A (en) * | 1967-02-06 | 1970-07-07 | Koppers Co Inc | Preparation of meta-rich cresols |
| US3933927A (en) * | 1970-03-16 | 1976-01-20 | Ethyl Corporation | Phenol transalkylation process |
| US4398048A (en) * | 1981-10-21 | 1983-08-09 | Uop Inc. | Preparation of 2,4,6-trialkylphenols |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291724B1 (en) * | 1997-09-24 | 2001-09-18 | General Electric Company | Suppression of highly alkylated phenols in the catalytic alkylation reaction of phenol |
| US6593501B2 (en) | 2000-09-18 | 2003-07-15 | Asahi Kasei Kabushiki Kaisha | Process for the preparation of 2,6-xylenol |
| CN108192053A (en) * | 2018-01-25 | 2018-06-22 | 杜广新 | A kind of method that high-performance Alkylphenolic Tackifying Resin is produced using phenol waste as raw material |
| CN108192053B (en) * | 2018-01-25 | 2020-10-13 | 杜广新 | Method for producing high-performance alkyl phenolic tackifying resin by taking phenol waste as raw material |
| US11485694B2 (en) | 2019-02-04 | 2022-11-01 | China Petroleum & Chemical Corporation | Dealklylation and transalkylation of mixed phenols to make cresols |
| US11767280B2 (en) | 2019-02-04 | 2023-09-26 | China Petroleum & Chemical Corporation | Process for making phenol and xylenes |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0119421A1 (en) | 1984-09-26 |
| DE3460271D1 (en) | 1986-08-14 |
| JPS6233216B2 (en) | 1987-07-20 |
| JPS59152340A (en) | 1984-08-31 |
| EP0119421B1 (en) | 1986-07-09 |
| DE3304663C1 (en) | 1984-06-20 |
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| FPAY | Fee payment |
Year of fee payment: 4 |
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| REMI | Maintenance fee reminder mailed | ||
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